CN115322317B - Scratch-resistant waterborne polyurethane resin for decorative paper and preparation method thereof - Google Patents
Scratch-resistant waterborne polyurethane resin for decorative paper and preparation method thereof Download PDFInfo
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- CN115322317B CN115322317B CN202210988812.6A CN202210988812A CN115322317B CN 115322317 B CN115322317 B CN 115322317B CN 202210988812 A CN202210988812 A CN 202210988812A CN 115322317 B CN115322317 B CN 115322317B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/40—High-molecular-weight compounds
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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Abstract
The invention discloses scratch-resistant aqueous polyurethane resin for decorative paper and a preparation method thereof, which belong to the technical field of coatings, and comprise a component A and a component B, wherein the component A comprises extinction aqueous polyurethane emulsion, a flatting agent and a defoaming agent; the component B is polyurethane curing agent; adding the extinction type polyester prepolymer into the aqueous solution of ethylenediamine sodium ethane sulfonate, stirring and mixing, then adding the hydroxyl type aqueous polyurethane prepolymer, stirring and mixing, and finally dripping ethylenediamine to remove the residual isocyanate groups to obtain extinction type aqueous polyurethane emulsion; nanometer gamma-Al 2 O 3 The modified extinction powder has better dispersion stability, is favorable for improving the cohesiveness, adhesive force and hardness of polyurethane resin, has better wear resistance, flexibility and color-developing property after the polyurethane resin is solidified into a film, has small light reflection, is favorable for presenting the original pattern color of decorative paper, and increases the quality of the decorative paper.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to scratch-resistant waterborne polyurethane resin for decorative paper and a preparation method thereof.
Background
The decorative paper is a common raw material in building material products, such as a low-pressure plate, a high-pressure plate, a fireproof plate, a base plate and the like used for furniture and cabinets, and a small amount of resin is impregnated or coated on the surface of the decorative paper after the decorative paper is printed with patterns, so that the patterns of the decorative paper can be clearly displayed, the hard elasticity and flexibility of the decorative paper are increased, the decorative paper does not need to be coated after being overlaid, and the decorative paper has the advantages of simple operation process, excellent surface performance, attractive patterns, low price, high temperature resistance, acid-base corrosion resistance and the like. The conventional solvent type resin paint generally adopts a volatile organic solvent, so that the environment is polluted greatly, and the aqueous polyurethane resin takes water as the solvent, so that the formaldehyde or toxic organic solvent is not volatilized, and the environment is protected more.
The decorative paper is easy to scratch in the subsequent plate processing process and the product using process, the attractiveness is affected, in order to increase the scratch resistance of the decorative paper, a scratch resistant agent and other filling materials are generally added into the resin coating, nano silicon dioxide is commonly used in the prior art, but the nano silicon dioxide is not easy to disperse, a cured paint film has certain light reflection property, the original pattern and color of the decorative paper cannot be reflected due to light reflection at a plurality of angles, fine scratches are easy to refract, the appearance is poor, and therefore, the scratch resistant aqueous polyurethane resin for the decorative paper with the extinction effect and the preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide scratch-resistant water-based polyurethane resin for decorative paper and a preparation method thereof, which are used for solving the problems in the background technology.
The aim of the invention can be achieved by the following technical scheme:
the scratch-resistant aqueous polyurethane resin for the decorative paper comprises a component A and a component B, wherein the component B is a polyurethane curing agent; the component A comprises the following raw materials in parts by mass:
60-78 parts of extinction waterborne polyurethane emulsion, 0.5-0.8 part of flatting agent and 0.5-0.8 part of defoaming agent.
Further, the extinction aqueous polyurethane emulsion is prepared by the following steps:
step one: neopentyl glycol, 2-dimethylolbutyric acid, trimethylolpropane and poly (1, 4-butanediol adipate) with molecular weight of 1000 are dried in vacuum and then added into a flask, then proper amount of acetone is added to reduce the viscosity of a reaction system, stirring is carried out for 15min at 50 ℃ and 250r/min, then toluene diisocyanate and dibutyltin dilaurate are added, the temperature is raised to 65 ℃ for reaction for 5h, triethylamine is added to adjust the pH value to 7-8 after the temperature is lowered to 50 ℃, and the acetone is distilled off in a rotating way, so that the hydroxyl type water-based polyurethane prepolymer is obtained.
Step two: vacuum drying 2, 2-hydroxymethyl butyric acid, polytetrahydrofuran ether glycol with molecular weight of 2000 and isophorone diisocyanate, then adding into a flask, dropwise adding dibutyl tin dilaurate, heating to 50 ℃ under the condition of magnetic stirring, heating to 70 ℃ for reaction for 1h, heating to 75 ℃ for reaction for 1h, heating to 80 ℃, adding epoxy resin for continuous reaction for 1h, adding triethylamine to adjust pH value to 7-8, cooling, adding modified extinction powder, performing ultrasonic dispersion for 10-15min, and performing shearing dispersion for 20-30min to obtain extinction type polyurethane prepolymer;
step three: adding the extinction type polyester prepolymer into an aqueous solution of sodium ethylenediamine ethanesulfonate with the mass fraction of 16%, stirring for 15-20min at the condition of 250-500r/min, then adding the hydroxyl type aqueous polyurethane prepolymer, stirring for 20-30min at the condition of 3500r/min, finally adopting a di-n-butylamine-acetone method to measure the content of unreacted isocyanate groups in a dropwise manner, and dropwise adding ethylenediamine to remove the residual isocyanate groups to obtain the extinction type aqueous polyurethane emulsion.
Further, neopentyl glycol, 2-dimethylolbutyric acid, trimethylolpropane, poly (1, 4-butylene adipate), acetone, toluene diisocyanate and dibutyltin dilaurate were used in an amount ratio of 85g:45g:45-55g:1000g:70-80g:210g:0.13g.
Further, the dosage ratio of 2, 2-hydroxymethyl butyric acid, polytetrahydrofuran ether glycol, isophorone diisocyanate, dibutyltin dilaurate, epoxy resin and modified matting agent is 90g:2000g:245g:0.15g:225g:180-200g.
Further, the dosage ratio of the hydroxyl type aqueous polyurethane prepolymer, the extinction type polyurethane prepolymer and the aqueous solution of sodium ethylenediamine-based ethanesulfonate is 12g:25g:12.5g.
Further, the modified matting powder is prepared by the steps of:
adding 3- (trimethoxysilyl) propyl methacrylate and absolute ethanol into a flask, stirring and mixing, and then adding nano gamma-Al into the flask 2 O 3 Refluxing for 1.5-2h under the condition of magnetic stirring, filtering, drying the filter cake at 60-80 ℃ and crushing to obtain the modified extinction powder.
Further, 3- (trimethoxysilyl) propyl methacrylate, absolute ethyl alcohol and nano gamma-Al 2 O 3 The dosage ratio of (2) is 10mL:18-20mL:7g.
Further, the leveling agent is Glide450.
Further, the defoamer was model Silok4600.
Further, the polyurethane curing agent is TDI or HDI.
The preparation method of the scratch-resistant aqueous polyurethane resin for the decorative paper comprises the following steps:
stirring and mixing the extinction aqueous polyurethane emulsion, the flatting agent and the defoamer to obtain a component A, and mixing the component A and the component B according to the proportion of 5-6: and mixing the materials according to the mass ratio of 1 to obtain the scratch-resistant aqueous polyurethane resin for the decorative paper.
The invention has the beneficial effects that:
the scratch-resistant aqueous polyurethane resin for the decorative paper has moderate leveling property and adhesiveness, has good wear resistance, flexibility and color spreading property after being cured into a film, is favorable for presenting the original pattern color of the decorative paper and increases the quality of the decorative paper.
Nanometer gamma-Al 2 O 3 The particle size of the nano silica is 20nm, the specific surface area is large, the dimensional stability is good, the particle size is close to that of the nano silica, but the hardness is larger than that of the nano silica. Nanometer gamma-Al 2 O 3 The surface of the material is provided with hydroxyl groups, after the 3- (trimethoxysilyl) methyl propyl acrylate is modified, the 3- (trimethoxysilyl) methyl propyl acrylate is hydrolyzed and then is mixed with nano gamma-Al 2 O 3 The surface Al-OH is condensed, so that the nano gamma-Al is grafted 2 O 3 And (3) finally preparing the modified extinction powder on the surface.
Nanometer gamma-Al 2 O 3 The modified extinction powder has better dispersion stability, and is beneficial to improving the cohesiveness, adhesive force and hardness of polyurethane resin. Epoxy resin is added in the preparation process of the extinction type polyurethane emulsion, the epoxy group is introduced into a system after ring opening, and hydroxyl reacts with isocyanate groupThe polyurethane resin has the advantages that a reticular structure is formed, the stability of the extinction type polyurethane prepolymer is improved, the settlement of modified extinction powder is further prevented, the glossiness and the contact angle of the cured polyurethane resin can be reduced, the pattern of the decorative paper is revealed, and the water resistance and the alkali resistance of the decorative paper are improved. Preparing hydroxyl-type water-based polyurethane prepolymer containing more hydroxyl groups, mixing the hydroxyl-type water-based polyurethane prepolymer with the extinction-type polyurethane prepolymer, so that the water solubility and leveling property of extinction-type water-based polyurethane emulsion can be improved, and then mixing with ethylenediamine sodium ethanesulfonate aqueous solution, so that the compatibility of the two prepolymer emulsions can be improved, the functions of an emulsifying agent and a chain extender can be provided, the solid content of the extinction-type water-based polyurethane emulsion can be improved, the drying speed of the extinction-type water-based polyurethane emulsion can be increased, and film forming and curing can be facilitated; because the curing speeds of the two polyurethane prepolymers are different, the cured polyurethane resin has micro unevenness, and the light reflection is further reduced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing extinction aqueous polyurethane emulsion, which comprises the following steps:
step one: into the flask, 300mL of 3- (trimethoxysilyl) propyl methacrylate and 540mL of absolute ethanol were added and mixed with stirring, and then 210g of nano gamma-Al was added into the flask 2 O 3 Refluxing for 1.5h under the condition of magnetic stirring, filtering, drying the filter cake at 60 ℃, and crushing to obtain the modified extinction powder.
Step two: 85g of neopentyl glycol, 45g of 2, 2-dimethylolbutyric acid, 45g of trimethylolpropane and 1000g of poly (1, 4-butanediol adipate) with the molecular weight of 1000 are dried in vacuum and then added into a flask, 70g of acetone is added to reduce the viscosity of a reaction system, the mixture is stirred for 15min at 50 ℃ and 250r/min, 210g of toluene diisocyanate and 0.13g of dibutyltin dilaurate are added to react for 5h at 65 ℃, triethylamine is added to adjust the pH value to 7 after the temperature is reduced to 50 ℃, and the acetone is distilled off in a rotating way to obtain the hydroxyl type water-based polyurethane prepolymer.
Step three: vacuum drying 90g of 2, 2-hydroxymethyl butyric acid, 2000g of polytetrahydrofuran ether glycol with the molecular weight of 2000 and 245g of isophorone diisocyanate, then adding into a flask, dropwise adding 0.15g of dibutyltin dilaurate, heating to 50 ℃ under the condition of magnetic stirring, reacting for 1h at 70 ℃ after 1h, reacting for 1h at 75 ℃, heating to 80 ℃, adding 225g of epoxy resin, continuously reacting for 1h, adding triethylamine to adjust the pH value to 7, cooling, adding 180g of modified extinction powder, performing ultrasonic dispersion for 10min, and shearing and dispersing for 20min to obtain extinction type polyurethane prepolymer;
step four: 2500g of extinction type polyester prepolymer is added into 1250g of sodium ethylenediamine ethanesulfonate aqueous solution with the mass fraction of 16%, stirring is carried out for 15min under the condition of 2500r/min, then 1200g of hydroxyl type aqueous polyurethane prepolymer is added, stirring is carried out for 20min under the condition of 3500r/min, finally unreacted isocyanate group content is measured by adopting a di-n-butylamine-acetone method in a dropwise manner, and ethylenediamine is added in a dropwise manner to remove residual isocyanate groups, thus obtaining extinction type aqueous polyurethane emulsion.
Example 2
Preparing extinction aqueous polyurethane emulsion, which comprises the following steps:
step one: into the flask, 300mL of 3- (trimethoxysilyl) propyl methacrylate and 570mL of absolute ethanol were added and mixed with stirring, and then 210g of nano gamma-Al was added into the flask 2 O 3 Refluxing for 1.8h under the condition of magnetic stirring, filtering, drying the filter cake at 70 ℃, and crushing to obtain the modified extinction powder.
Step two: 85g of neopentyl glycol, 45g of 2, 2-dimethylolbutyric acid, 50g of trimethylolpropane and 1000g of poly (1, 4-butanediol adipate) with the molecular weight of 1000 are dried in vacuum and then added into a flask, 75g of acetone is added to reduce the viscosity of a reaction system, the mixture is stirred for 15min at 50 ℃ and 250r/min, 210g of toluene diisocyanate and 0.13g of dibutyltin dilaurate are added, the temperature is raised to 65 ℃ to react for 5h, triethylamine is added to adjust the pH value to 7.5 after the temperature is reduced to 50 ℃, and the acetone is distilled off in a rotating way, so that the hydroxyl type water-based polyurethane prepolymer is obtained.
Step three: vacuum drying 90g of 2, 2-hydroxymethyl butyric acid, 2000g of polytetrahydrofuran ether glycol with the molecular weight of 2000 and 245g of isophorone diisocyanate, then adding into a flask, dropwise adding 0.15g of dibutyltin dilaurate, heating to 50 ℃ under the condition of magnetic stirring, reacting for 1h at 70 ℃ after 1h, reacting for 1h at 75 ℃, heating to 80 ℃, adding 225g of epoxy resin, continuously reacting for 1h, adding triethylamine to adjust the pH value to 7.5, cooling, adding 190g of modified extinction powder, performing ultrasonic dispersion for 12min, and performing shearing dispersion for 25min to obtain extinction type polyurethane prepolymer;
step four: 2500g of extinction type polyester prepolymer is added into 1250g of sodium ethylenediamine ethanesulfonate aqueous solution with the mass fraction of 16%, stirred for 18min under the condition of 400r/min, then 1200g of hydroxyl type aqueous polyurethane prepolymer is added, stirred for 25min under the condition of 3500r/min, finally unreacted isocyanate group content is measured by adopting a di-n-butylamine-acetone method in a dropwise manner, and ethylenediamine is added dropwise to remove residual isocyanate groups, thus obtaining extinction type aqueous polyurethane emulsion.
Example 3
Preparing extinction aqueous polyurethane emulsion, which comprises the following steps:
step one: into a flask, 300mL of 3- (trimethoxysilyl) propyl methacrylate and 600mL of absolute ethanol were added and mixed with stirring, and then 210g of nano gamma-Al was added to the flask 2 O 3 Refluxing for 2h under the condition of magnetic stirring, filtering, drying the filter cake at 80 ℃, and crushing to obtain the modified extinction powder.
Step two: 85g of neopentyl glycol, 45g of 2, 2-dimethylolbutyric acid, 55g of trimethylolpropane and 1000g of poly (1, 4-butanediol adipate) with the molecular weight of 1000 are dried in vacuum and then added into a flask, 80g of acetone is added to reduce the viscosity of a reaction system, the mixture is stirred for 15min at 50 ℃ and 250r/min, 210g of toluene diisocyanate and 0.13g of dibutyltin dilaurate are added, the temperature is raised to 65 ℃ to react for 5h, triethylamine is added to adjust the pH value to 8 after the temperature is reduced to 50 ℃, and the acetone is distilled off in a rotating way to obtain the hydroxyl type water-based polyurethane prepolymer.
Step three: vacuum drying 90g of 2, 2-hydroxymethyl butyric acid, 2000g of polytetrahydrofuran ether glycol with the molecular weight of 2000 and 245g of isophorone diisocyanate, then adding into a flask, dropwise adding 0.15g of dibutyltin dilaurate, heating to 50 ℃ under the condition of magnetic stirring, reacting for 1h at 70 ℃ after 1h, reacting for 1h at 75 ℃, heating to 80 ℃, adding 225g of epoxy resin, continuously reacting for 1h, adding triethylamine to adjust the pH value to 8, cooling, adding 200g of modified extinction powder, performing ultrasonic dispersion for 15min, and performing shearing dispersion for 30min to obtain an extinction polyurethane prepolymer;
step four: 2500g of extinction type polyester prepolymer is added into 1250g of sodium ethylenediamine ethanesulfonate aqueous solution with the mass fraction of 16%, stirred for 20min under the condition of 500r/min, then 1200g of hydroxyl type aqueous polyurethane prepolymer is added, stirred for 30min under the condition of 3500r/min, finally unreacted isocyanate group content is measured by adopting a di-n-butylamine-acetone method in a dropwise manner, and ethylenediamine is added dropwise to remove residual isocyanate groups, thus obtaining extinction type aqueous polyurethane emulsion.
Example 4
The preparation of the scratch-resistant aqueous polyurethane resin for the decorative paper comprises the following steps:
the extinction aqueous polyurethane emulsion prepared in example 1, a Glide450 leveling agent and a Silok4600 defoamer are stirred and mixed to obtain a component A, and then the component A and TDI are mixed according to a ratio of 5: and mixing the materials according to the mass ratio of 1 to obtain the scratch-resistant aqueous polyurethane resin for the decorative paper.
Example 5
The preparation of the scratch-resistant aqueous polyurethane resin for the decorative paper comprises the following steps:
the matt aqueous polyurethane emulsion prepared in example 2, glide450 leveling agent and Silok4600 defoamer were stirred and mixed to obtain component a, and components a and TDI were further mixed according to 6: and mixing the materials according to the mass ratio of 1 to obtain the scratch-resistant aqueous polyurethane resin for the decorative paper.
Example 6
The preparation of the scratch-resistant aqueous polyurethane resin for the decorative paper comprises the following steps:
the matt aqueous polyurethane emulsion prepared in example 3, glide450 leveling agent and Silok4600 defoamer were stirred and mixed to obtain component a, and components a and HDI were further mixed according to 5: and mixing the materials according to the mass ratio of 1 to obtain the scratch-resistant aqueous polyurethane resin for the decorative paper.
Comparative example 1: on the basis of example 3, nano gamma-Al is prepared 2 O 3 Instead of nano silica, the rest of the procedure remained unchanged, and a polyurethane emulsion was prepared and a polyurethane resin was prepared according to the method of example 5.
Comparative example 2: polyurethane emulsion was prepared without adding hydroxyl type aqueous polyurethane prepolymer on the basis of example 3, and then polyurethane resin was prepared according to the method of example 5.
Comparative example 3: on the basis of example 3, the modified matting powder was directly mixed with a hydroxyl-type aqueous polyurethane prepolymer, and then emulsified with an aqueous solution of sodium ethylenediamine-based ethanesulfonate according to the method of step 4 to prepare a polyurethane emulsion, and then a polyurethane resin was prepared according to the method of example 5.
The polyurethane emulsions prepared in examples 4 to 6 and comparative examples 1 to 3 were first allowed to stand for 24 hours to observe the dispersion of the polyurethane emulsions. Among them, the polyurethane emulsions prepared in example 1-example 3, comparative example 1 and comparative example 2 were uniform and free of sedimentation particles, whereas the polyurethane emulsion in comparative example 2 showed sedimentation particles, indicating that the polyurethane emulsion in example 1-example 3 was better in dispersibility.
The polyurethane resins of examples 4 to 5 and comparative examples 1 to 3 were coated on the surfaces of PVC decorative papers, respectively, to prepare test pieces, the film thickness of which was 35.+ -.5. Mu.m, and the gloss, pencil hardness and adhesion of the films of each test piece were measured in accordance with GB/T1743-1979, GB/T6739-2006 and GB/T9286-1998, and the results are shown in Table 1:
TABLE 1
| Project | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Gloss level | 2.2 | 2.2 | 2.3 | 8 | 16 | 24 |
| Hardness of pencil | 4H | 4H | 4H | 3H | 3H | H |
| Adhesion force | Level 0 | Level 0 | Level 0 | Level 1 | Level 1 | Level 1 |
As can be seen from Table 1, the polyurethane resins prepared in examples 4 to 6 have good gloss, hardness and abrasion resistance.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The scratch-resistant water-based polyurethane resin for the decorative paper is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by mass:
60-78 parts of extinction waterborne polyurethane emulsion, 0.5-0.8 part of flatting agent and 0.5-0.8 part of defoaming agent;
the component B is a polyurethane curing agent;
the extinction waterborne polyurethane emulsion is prepared through the following steps:
step one: mixing vacuum-dried 2, 2-dimethylolbutyric acid, polytetrahydrofuran ether glycol and isophorone diisocyanate, adding dibutyl tin dilaurate, heating to 50 ℃ for reaction for 1h under the condition of magnetic stirring, heating to 70 ℃ for reaction for 1h, heating to 75 ℃ for reaction for 1h, heating to 80 ℃, adding epoxy resin for continuous reaction for 1h, adding triethylamine for regulating the pH value to 7-8, cooling, adding modified extinction powder, performing ultrasonic dispersion, and shearing and dispersing to obtain an extinction polyurethane prepolymer;
step two: adding the extinction type polyester prepolymer into the aqueous solution of ethylenediamine sodium ethane sulfonate, stirring and mixing, then adding the hydroxyl type aqueous polyurethane prepolymer, stirring and mixing, finally adopting a di-n-butylamine-acetone method to measure the content of unreacted isocyanate groups in a dropwise manner, and dropwise adding ethylenediamine to remove the residual isocyanate groups to obtain extinction aqueous polyurethane emulsion;
the hydroxyl aqueous polyurethane prepolymer is prepared by the following steps:
vacuum drying neopentyl glycol, 2-dimethylolbutyric acid, trimethylolpropane and poly (1, 4-butanediol adipate) and adding the dried materials into a flask, adding acetone, stirring for 15min at 50 ℃ and 250r/min, then adding toluene diisocyanate and dibutyltin dilaurate, heating to 65 ℃ for reacting for 5h, cooling to 50 ℃, adding triethylamine, regulating the pH value to 7-8, and rotationally steaming to remove the acetone to obtain a hydroxyl type water-based polyurethane prepolymer;
the modified extinction powder is prepared through the following steps:
adding 3- (trimethoxysilyl) propyl methacrylate and absolute ethanol into a flask, stirring and mixing, and then adding nano gamma-Al 2 O 3 Refluxing for 1.5-2h under the condition of magnetic stirring, filtering, drying a filter cake, and crushing to obtain the modified extinction powder.
2. The scratch-resistant aqueous polyurethane resin for decorative paper according to claim 1, wherein the dosage ratio of neopentyl glycol, 2-dimethylolbutyric acid, trimethylolpropane, poly (1, 4-butylene adipate), acetone, toluene diisocyanate and dibutyltin dilaurate is 85g:45g:45-55g:1000g:70-80g:210g:0.13g.
3. The scratch-resistant aqueous polyurethane resin for decorative paper according to claim 1, wherein the dosage ratio of the 2, 2-dimethylolbutyric acid, polytetrahydrofuran ether glycol, isophorone diisocyanate, dibutyltin dilaurate, epoxy resin and modified matting agent in the step one is 90g:2000g:245g:0.15g:225g:180-200g.
4. The scratch-resistant aqueous polyurethane resin for decorative paper according to claim 1, wherein the dosage ratio of the hydroxyl aqueous polyurethane prepolymer, the extinction type polyurethane prepolymer and the aqueous solution of sodium ethylenediamine-based ethanesulfonate in the second step is 12g:25g:12.5g.
5. The scratch-resistant aqueous polyurethane resin for decorative paper according to claim 1, wherein the 3- (trimethoxysilyl) propyl methacrylate, absolute ethyl alcohol and nano gamma-Al 2 O 3 The dosage ratio of (2) is 10mL:18-20mL:7g.
6. The scratch-resistant aqueous polyurethane resin for decorative paper according to claim 1, wherein the leveling agent is Glide450.
7. The scratch-resistant aqueous polyurethane resin for decorative paper according to claim 1, wherein the polyurethane curing agent is TDI or HDI.
8. The method for producing a scratch-resistant aqueous polyurethane resin for decorative paper according to any one of claims 1 to 7, comprising the steps of:
stirring and mixing the extinction aqueous polyurethane emulsion, the flatting agent and the defoamer to obtain a component A, and mixing the component A and the component B according to the proportion of 5-6: and mixing the materials according to the mass ratio of 1 to obtain the scratch-resistant aqueous polyurethane resin for the decorative paper.
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